JP2002504605A - Method for producing a polymer blend from an aminonitrile and a thermoplastic polymer - Google Patents

Abstract

  (57) [Summary] Of a polymer blend by reaction of at least one aminonitrile with water, in the presence of a thermoplastic polymer and optionally other polyamide-forming monomers, the following steps: (1) a temperature of 90-400 ° C., Reacting at least one aminonitrile with water under conditions of a pressure of 35 × 10 6 Pa to obtain a reaction mixture; At this temperature and pressure to obtain a first gas phase and a first liquid phase or a first solid phase, or a mixture of the first solid phase and the first liquid phase. And separating the first gas phase and a first liquid phase or a first solid phase, or a mixture of the first liquid phase and the first solid phase; and 3) a first liquid phase or a first solid phase, or Mixing the mixture of the first liquid phase and the first solid phase with a gas or liquid phase comprising water at a temperature of 150-370 ° C. and a pressure of 0.1-30 × 10 6 Pa to obtain a polymer blend. A production method characterized in that the thermoplastic polymer and, if necessary, another polyamide-forming monomer are added in at least one of the steps.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001] The present invention relates to a novel method of making a polymer blend by reacting an aminonitrile in the presence of water, a thermoplastic polymer and optionally other polyamide-forming monomers.

[0002] Homopolymer-based plastics have the disadvantage of limiting their potential for use. By the polymer blend, the physical properties of the plastic can be improved by combining blended objects having different properties. This is why, for example, blends of polyamides such as polyarylene ether sulfone or polyetherimide and amorphous plastics are obtained.

[0003] Polyamides can be obtained in a very large number of ways. The most important reaction for the production of polyamides is the hydrolytic ring-opening polymerization of lactams. One mode of this method which can be performed industrially is disclosed, for example, in DE-A 43 16 683.

[0004] Alternatively, there is a method in which a polyamide is obtained from aminonitrile, whereby other raw materials can be used. For example, DE-A 19709390, which was not published on the priority date of the present invention, discloses continuous and batch processes for producing polyamides from aminonitrile and water at high temperature and pressure.

To obtain polyamide blends, US Pat. No. 3,729,527 proposes, in particular, the polymerization of ε-caprolactam in the presence of polyarylene ether sulfone. DE-A 41 02 996 likewise has an amorphous polymer, for example polysulfone,
It has been proposed to polymerize lactams in the presence of styrene copolymers to obtain polyphenylene ether, polyetherimide, polyamideimide or polymer blends. The polymerization is initiated using a strong base.

When the polymer blend components are mixed in the melt, for example in an extruder, a compatibilizer is usually added to them. EP-A 0 374 988, McGrath et al., Polym. Pre.
14, 1032 (1973) or Corning et al., Makromol. Chem. Macromol. Symp. 7
According to 5, 159 (1993), useful compatibilizers are copolymers of polyamide and polyarylene ether sulfone segments, which dissolve polyarylene ether sulfone in a lactam melt and react in the presence of a strong base. The lactam is obtained by polymerizing the lactam while excluding water.

A study of anionic polymerization of lactams in an extruder in the presence of polyetherimide or polysulfone was performed by Van Buskirk et al., Polym. Prepr. 29 (1), 557 (1998).

[0008] All of the above methods utilize lactams or polyamides obtained from lactams for making blends of polyamide and thermoplastic polymer.

The above method has the disadvantage that the polymer chains of the thermoplastic polymer are degraded by the action of anions in the reaction mixture. In addition, anionic polymerization requires special technical means to control the degree of polymerization. The reason is believed to be that the reaction is generally very fast and the viscosity increases in a very short time. As a result, it is difficult to obtain a product having a well-defined structure, that is, a chain length or a viscosity,
Or impossible. In addition, this product contains catalyst residues and degradation, or often unremovable by-products. When polymerizing in an extruder, it is often not possible to achieve complete conversion and to obtain a final product containing residual monomers. further,
In many cases, the only product obtained is dark, for example brown.

[0010] Schnablegger ea al., Acta Polym. 46, 307 (1995) discloses the reaction of ε-caprolactam with polyarylene ether sulfones containing aminophenyl end groups. The polymerization reaction is initiated by the reaction of this amino group with ε-caprolactam by ring opening. This reaction is performed with the exclusion of water, and phosphoric acid can be used as a catalyst. The disadvantage of this method is that it is difficult to increase the purity of the polyarylene ether sulfone containing two aminophenyl end groups per polymer chain.

It is therefore an object of the present invention to provide an improved method for producing different thermoplastic and polyamide-based compositions (polymer blends) without the disadvantages of existing methods.

The present inventors have determined that an object of the present invention is to produce a polyamide by reacting at least one aminonitrile with water, preferably in the presence of a thermoplastic polymer and optionally other polyamide-forming monomers. (1) a temperature of 90 to 400 ° C. and a pressure of 0.1 to 35 × 10 ⁶ Pa, preferably a β-zeolite catalyst, a plate-like silicate catalyst, or 70 to 100% by mass. At least one aminonitrile in the presence of a Bronsted acid catalyst selected from titanium dioxide catalysts comprising anatase and 0-30% by mass of rutile, up to 40% by mass of which may be replaced by tungsten oxide. Reacting with water to obtain a reaction mixture, (2) further reacting the reaction mixture with a β-zeolite catalyst, a plate-like silicate catalyst,
Or 70 to 100% by weight of anatase and 0 to 30% by weight of rutile;
In the presence of a Brönsted acid catalyst selected from titanium dioxide catalysts whose mass% may be replaced by tungsten oxide, a temperature of 150 to 400 ° C. and a step (1)
A) reacting at lower pressure conditions, wherein the temperature and pressure are reduced by the first gas phase and the first liquid phase or the first solid phase, or the first solid phase and the first liquid phase; Selecting to obtain a mixture, and separating the first gas phase and the first liquid phase or the first solid phase, or a mixture of the first liquid phase and the first solid phase; And (3) converting the first liquid phase or the first solid phase, or a mixture of the first liquid phase and the first solid phase, to a temperature of 150 to 370 ° C. and 0.1 to 30 × 10 ⁶ Pa Obtaining a polymer blend by mixing with a liquid phase containing water under the conditions of the pressure, and adding the thermoplastic polymer and optionally other polyamide-forming monomers in one or more of the steps. It has been found that this can be achieved by a characteristic manufacturing method.

The above method further comprises the following steps: (4) post-condensing the polymer blend at a temperature of 200-350 ° C. at a lower pressure than in step (3), wherein the temperature and pressure are: A second water- and ammonia-containing gas phase and a second
Or a mixture of a second liquid phase and a second solid phase, each phase comprising a polymer blend.

Further, the present invention is a preferably continuous process for producing a polymer blend by reacting at least one aminonitrile with water in the presence of a thermoplastic polymer and optionally other polyamide-forming monomers, comprising: 1) Under the conditions of a temperature of 90 to 400 ° C. and a pressure of 0.1 to 35 × 10 ⁶ Pa, preferably a β-zeolite catalyst, a plate-like silicate catalyst, or 70 to 100% by mass of anatase and 0 to 30% by mass. Reacting at least one aminonitrile with water in the presence of a Bronsted acid catalyst selected from titanium dioxide catalysts containing up to 40% by weight of rutile and up to 40% by weight of tungsten oxide optionally substituted by tungsten oxide A step of obtaining a mixture, (2) further adding a β-zeolite catalyst, a plate-like silicate catalyst,
Or 70 to 100% by weight of anatase and 0 to 30% by weight of rutile;
In the presence of a Brönsted acid catalyst selected from titanium dioxide catalysts whose mass% may be replaced by tungsten oxide, a temperature of 150 to 400 ° C. and a step (1)
A) reacting at lower pressure conditions, wherein the temperature and pressure are reduced by the first gas phase and the first liquid phase or the first solid phase, or the first solid phase and the first liquid phase; Selecting to obtain a mixture, and separating the first gas phase and the first liquid phase or the first solid phase, or a mixture of the first liquid phase and the first solid phase; And (3) converting the first liquid phase or the first solid phase, or a mixture of the first liquid phase and the first solid phase, to a β-zeolite catalyst, a plate-like silicate catalyst, or 70 to 100 mass %
In the presence of a Bronsted acid catalyst selected from titanium dioxide catalysts comprising up to 40% by weight of anatase and 0-30% by weight of rutile, up to 40% by weight of tungsten oxide, The post-condensation is carried out at a lower pressure than in step (2), the temperature and pressure being reduced to a second water- and ammonia-containing gas phase and a second
Selecting a liquid phase or a second solid phase, or a mixture of a second liquid phase and a second solid phase, wherein each phase comprises a polymer blend. An object of the present invention is to provide a production method characterized by adding the thermoplastic polymer and, if necessary, other polyamide-forming monomers in the above steps.

According to the invention, amino nitriles, water, thermoplastic polymers and, if desired, other polyamide-forming monomers are used as starting materials. In addition to utilizing aminonitrile as a starting material for polyamide formation, the present invention provides for the production of a polymer blend during the reaction of the aminonitrile rather than after the production of the polyamide.
The advantage is that finely dispersed blends with improved product properties can be produced in an inexpensive manner.

Preferably, a thermoplastic polymer is added to steps (3) and / or (4) and no other monomers are introduced.

The basic method for producing pure polyamides is disclosed in the prior application DE-A 1970390, which has not been published on the priority date of the present invention.

The aminonitrile in the mixture may be mainly any aminonitrile, that is, a compound having both at least one amino group and at least one nitrile group. ω-aminonitrile is preferred, especially ω-aminoalkylnitrile having 4 to 12 carbon atoms, more preferably 4 to 9 carbon atoms in the alkylene moiety, or amino having 8 to 13 carbon atoms. Preferably, the aminoalkylaryl is an alkylaryl nitrile wherein the tolyl has an alkylene group which is at least one carbon atom between the aromatic unit and the amino and nitrile groups. In particular, preferred aminoalkylaryl nitriles are
They have an amino group and a nitrile group at the 1,4-position mutually.

As ω-aminoalkylnitrile, a straight-chain ω-aminoalkylnitrile containing an alkylene moiety (—CH ₂ —), preferably containing 4 to 12, more preferably 4 to 9 carbon atoms, such as, for example, 6-amino-1-cyanopentane (6-aminocapronitrile), 7-amino-1-cyanohexane, 8-amino-1-cyanoheptane, 9-amino-1-cyanooctane, 10-amino-1- Preference is given to using cyanononane, in particular 6-aminocapronitrile.

6-Aminocapronitrile is generally prepared by known methods, for example DE-A 83693.
8, obtained by hydrogenating adiponitrile according to the method described in DE-A 848 654 or US Pat. No. 5,151,543.

Of course, it is also possible to use a mixture of aminonitrile or a mixture of aminonitrile and other comonomers (eg caprolactam) or a mixture as defined below.

[Polyamide-forming monomers] Suitable other polyamide-forming monomers include the following:
For example, dicarboxylic acids such as alkanedicarboxylic acids having 6 to 12, especially 6 to 10, carbon atoms, such as adipic acid, pimelic acid, suberic acid, azelaic acid or sebacic acid, furthermore terephthalic acid and isophthalic acid; 8 pieces of diamines such C _{4 ~ 12} alkyl diamine with a carbon atom, eg if hexamethyl diamine, tetramethylenediamine or octamethylenediamine, further m- xylylenediamine, bis (4-aminophenyl) methane,
2,2-bis (4-aminophenyl) propane or bis (4-aminocyclohexyl) methane, 2,2-bis (4-aminophenyl) propane or bis (aminocyclohexyl) methane; and dicarboxylic acid and diamine itself Any suitable combination but interrelated, advantageously hexamethylene diammonium adipate, hexamethylene diammonium terephthalate or tetramethylene diammonium adipate, preferably hexamethylene diammonium adipate, hexamethylene diammonium terephthalate The mixture is an equivalent ratio to

Polycaprolactam, polyamides formed from caprolactam, hexamethylenediamine, and also adipic acid, isophthalic acid and / or terephthalic acid are of particular industrial importance. It is a preferred embodiment to use ε-caprolactam and hexamethylene diammonium adipate (66 salt).

In a particularly preferred embodiment, especially when copolymerized polyamides or branched or chain-extended polyamides are to be produced, the following mixtures are used instead of pure 6-aminocapronitrile: 50 to 99.99 mass %, Preferably 80 to 90% by weight of 6-aminocapronitrile, 0.01 to 50% by weight, preferably 1 to 30% by weight of C ₄ -C ₁₀ -α, ω-aliphatic dicarboxylic acid, C ₈ -C ₁₂ - aromatic dicarboxylic acids and C ₅ -C ₈ - Shikuroa least one dicarboxylic acid selected from the Le dicarboxylic acid, 0 to 50 wt%, preferably from 0.1 to 30% by weight carbon atoms Α of 4 to 10,
ω-diamine, 0 to 50% by mass, preferably 0 to 30% by mass of α, ω-C ₂ -C ₁₂ -dinitrile, 0 to 50% by mass, preferably 0 to 30% by mass of α, ω-C ₅ -C ₁₂ - amino acids or the corresponding lactams, 0-10 wt% of at least one inorganic acid or salt thereof (provided that the total of the individual percentages by weight is 100%).

Suitable dicarboxylic acids are C ₄ -C ₁₀ -α, ω-aliphatic dicarboxylic acids such as succinic, glutaric, adipic, pimelic, suberic, azelaic and sebacic acids, preferably adipine San'oyobi sebacic acid, especially adipic acid), C ₈ -C ₁₂ - aromatic dicarboxylic acids (e.g., terephthalic acid), and C ₅ -C ₈ - cycloalkyl alkane dicarboxylic acids (e.g., cyclohexane dicarboxylic acid).

Preferred examples of the α, ω-diamine having 4 to 10 carbon atoms include tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, and decamethylenediamine. And preferably hexamethylenediamine.

Further, salts of the above-mentioned dicarboxylic acids and diamines, in particular, salts of adipic acid and hexamethylenediamine known as 66 salts can also be used.

As α, ω-C ₂ -C ₁₂ -dinitrile, preferably aliphatic dinitrile, for example, 1,4-dicyanobutane (adiponitrile), 1,5-cyanopentane,
6-dicyanohexane, 1,7-dicyanoheptane, 1,8-dicyanooctane, 1,9-dicyanononane, 1,10-dicyanodecane, particularly preferably adiponitrile are used.

If necessary, it is also possible to use diamines, dinitrile and aminonitrile derived from branched alkylene, arylene or alkylarylene compounds.

As α, ω-C ₅ -C ₁₂ -amino acids, 5-aminopentanoic acid, 6-aminohexanoic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid, 10-aminodecanoic acid, Either 11-aminoundecanoic acid or 12-aminododecanoic acid, preferably 6-aminohexanoic acid, can be used.

The compounds mentioned above can also be used in the form of a mixture.

Thermoplastic Polymers Suitable thermoplastic polymers are aminonitrile, mixtures with other polyamide-forming monomers, or all polymers soluble in the reaction mixture thereof, which do not adversely affect the polymerization reaction. According to the present invention, dissolving means obtaining a melt that is transparent to an observer, that is, that the thermoplastic polymer A may be physically dissolved or may be present in a finely dispersed form. means.

Suitable amorphous polymers are polyarylene ethers such as polyarylene ether sulfone or polyphenylene ether, polyetherimide, polyamideimide, polystyrene and styrene copolymers such as styrene / acrylonitrile copolymer, styrene / diene copolymer. Elastic graft copolymers based on polymers, dienes or acrylate rubbers, such as ABS (acrylonitrile / butadiene / styrene), ASA (acrylonitrile / styrene / acrylate) or AES (
Acrylonitrile / ethylene / styrene) or other ethylene copolymers. A mixture of different polymers A can also be dissolved.

General formula (I):

[0035]

Embedded image [Wherein, t and q in the formula each represent 0, 1, 2 or 3].

T, Q and Z may be different independently of one another. They are either chemical bond or _{-O -, - SO 2 -,} - S-, C = O, it may be a group selected from -N = N-and S = O. Furthermore, T, Q and Z have the general formula -R ^a C = CR ^b - or -CR ^c R ^d - {However, R ^a and R ^b represent each hydrogen or C ₁ -C ₁₀ alkyl, R ^c and R hydrogen ^d are each, C ₁ -C ₁₀ alkyl (e.g., methyl, ethyl, n- propyl, isopropyl, tert- butyl or n- hexyl), C ₁ ~C _{1 0} alkoxy (e.g., methoxy, ethoxy, n- propoxy , isopropoxy or n- butoxy), C ₆ -C ₁₈ aryl (e.g., may be a group represented by represents a phenyl or naphthyl)}. R ^c and R ^d may be bonded together with a carbon atom bonded thereto to form a cycloalkyl ring having 4 to 7 carbon atoms. Of these, cyclopentyl and cyclohexyl are preferred. The cycloalkyl ring, one or more, preferably may be substituted with two or three C ₁ -C ₆ alkyl group. The substituent on the cycloalkyl ring is preferably methyl. T, Q
And Z are each _{-O -, - SO 2 -,} C = O, preferably used polyarylene ether is a group table in a chemical bond or the formula -CR ^c R ^d. The groups R ^c and R ^d are preferably hydrogen and methyl. At least one of the groups T, Q and Z
One is —SO ₂ — or C ＝ O. If both t and q are 0, Z is -SO ₂ - or C = O, preferably -SO ₂ - is. Ar and Ar ¹ are each a C ₆ -C ₁₈ aryl, for example 1,5-naphthyl, 1,6-naphthyl, 2,7-naphthyl, 1,5-anthryl, 9,10-anthryl, 2,6-anthryl , 2,7-
Represents anthryl or biphenyl, especially phenyl. These aryl groups are preferably unsubstituted. However, it may have one or more, for example two, substituents. Suitable substituents are C ₁ -C ₁₀ alkyl (eg, methyl, ethyl, n-propyl, isopropyl, tert-butyl or n-hexyl), C ₆ -C ₁₈ aryl (eg, phenyl or naphthyl), (For example, methoxy, ethoxy, n- propoxy, isopropoxy or n- butoxy) ₁ -C ₁₀ alkoxy, and halogen. Of these, methyl, phenyl, methoxy and chlorine are preferred.

Suitable repeating units are shown below:

[0038]

Embedded image

Embedded image

Polyarylene ethers containing the repeating unit (I1), (I2) or (I8) are particularly preferred. These are, for example, polyarylene ethers containing 0 to 100 mol% of the repeating unit (I1) and 0 to 100 mol% of the repeating unit (I2).

Polyarylene ether is a copolymer or block copolymer containing polyarylene ether segments and segments of other thermoplastic polymers, such as polyesters, aromatic polycarbonates, polyester carbonates, polysiloxanes, polyimides or polyetherimides. There may be. The number average molecular weight of the graft in this block or copolymer is generally from 1000 to 30000 g / mol. Blocks having different structures may be arranged alternately or randomly. The amount by mass of the polyarylene ether in the copolymer or block copolymer is
In general, it is at least 10% by weight and may be up to 97% by weight. 9
Copolymers or block copolymers containing up to 0% by weight of polyarylene ether are preferred. Copolymers or block copolymers containing from 20 to 80% by weight of polyarylene ether are particularly preferred.

[0041] Other suitable polyarylene ethers are those modified with monomers containing acidic or anhydride groups. Such polyarylene ethers can be obtained, for example, starting from the corresponding monomers containing acidic and / or anhydride groups.
These monomers can also be obtained by grafting to a polyarylene ether chain. Suitable acidic groups are carboxylic, sulfonic and phosphoric groups. Particular preference is given to polyarylene ether sulfones containing acidic groups which are continuously or randomly dispersed in the polymer chain, which acid groups may be bonded, for example, to an arylene group or an alkylene intermediate. For example, a polyarylene ether sulfone modified with fumaric acid, maleic acid, maleic anhydride or particularly preferably with 4,4′-dihydroxyvaleric acid is suitable. Examples of such polyarylene ether sulfones are disclosed, for example, in EP-A 0 185 237.

A mixture of two or more different polyarylene ether sulfones may be used.

In general, the polyarylene ether has a number average molecular weight _Mn of 5000 to 60000 g / mol and a relative viscosity of 0.20 to 0.95 dl / g. Depending on the solubility of this polyarylene ether, the relative viscosities are measured at 20 to 25 ° C. in a 1% strength by weight N-methylpyrrolidone solution, a mixture of phenol and dichlorobenzene or a 96% strength sulfuric acid.

The polyarylene ether containing the repeating unit I is known per se and can be obtained by a known method.

These are formed, for example, by condensing an aromatic bishalogen compound and an alkali metal double salt of aromatic bisphenol. These can also be obtained by, for example, automatically condensing an alkali metal salt of an aromatic halophenol in the presence of a catalyst. Polyarylene ethers containing a carbonyl function can also be obtained by electrophilic (Friedel-Crafts) polycondensation. In the electrophilic polycondensation, by reacting the dicarbonyl chloride of phosgene with an aromatic compound containing two hydrogen atoms that can be substituted for the electrophilic substituent, or by converting both the acid chloride group and the displaceable hydrogen atom A carbonyl bridge is formed by automatically condensing the aromatic carbonyl chloride containing the carbonyl chloride.

Preferred processing conditions for the synthesis of polyarylene ethers include, for example, EP-A011
3112 and EP-A0135130. It is particularly preferred to react the monomers in an aprotic solvent (especially N-methylpyrrolidone) in the presence of an anhydrous alkali metal carbonate (especially potassium carbonate). In many cases, it has proven effective to react this monomer in the melt.

The polyarylene ethers of the general formula I are, for example, hydroxyl, chlorine,
It may contain terminal groups such as alkoxy, preferably methoxy, phenoxy, amino or anhydride, or a mixture of the above terminal groups.

The thermoplastic polymer A may also be a compound based on substituted, in particular disubstituted polyphenylene ethers, wherein one unit of ether oxygen is bonded to an adjacent unit of the benzene nucleus. It is preferable to use a polyphenylene ether substituted at the 2- and / or 6-position to this oxygen atom.

Examples of the substituent include halogen (for example, chlorine or bromine), and those having 20 carbon atoms.
Long-chain alkyls (eg, lauryl or stearyl), and short-chain alkyls having 1-4 carbon atoms, preferably containing no α-disposed tertiary hydrogen atoms, such as methyl, Ethyl, propyl or butyl. The alkyl group may be mono- or poly-substituted with halogen (eg, chlorine or bromine) or with hydroxyl. Another example of a possible substituent is alkoxy (preferably having 1 to 4 carbon atoms) or mono- or poly-substituted by halogen and / or C ₁ -C ₄ alkyl as described above. And phenyl which may be used. Copolymers of different phenols, for example 2,6
Copolymers of -dimethylphenol and 2,3,6-trimethylphenol are also suitable. Mixtures of different polyphenylene ethers can of course also be used.

Examples of polyphenylene ethers that may be used according to the invention include: poly (2,6-dilauryl-1,4-phenylene ether), poly (2,6-diphenyl-1) , 4-phenylene ether), poly (2,6-dimethoxy-1,4-phenylene ether), poly (2,6-diethoxy-1,4-phenylene ether), poly (2-methoxy-6-ethoxy-1) , 4-phenylene ether), poly (2-ethyl-6-stearyloxy-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether), poly (2-methyl-6- Phenyl-1,4-phenylene ether), poly (2,6-dibenzyl-1,4-phenylene ether), poly (2-ethoxy-1,4-phenylene) Niren'eteru), poly (2-chloro-1,4-phenylene ether), poly (2,5-dibromo-1,4-phenylene ether).

Preference is given to using the following polyphenylene ethers which are substituted by alkyl having 1 to 4 carbon atoms: poly (2,6-dimethyl-1,4-phenylene ether), poly (2,6- Diethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), poly (2-methyl-6-propyl-1,4-phenylene ether), poly (2 6-dipropyl-1,4-phenylene ether), and poly (2-ethyl-6-propyl-1,4-phenylene ether).

For the purposes of the present invention, polyphenylene ethers are understood to be modified with monomers such as, for example, fumaric acid, maleic acid or maleic anhydride.

Such polyphenylene ethers are disclosed in particular in WO 87/00540.

The polyphenylene ether used in the composition has, in particular, a weight-average molecular weight M _w of about 8000 to 70000, preferably about 12000 to 50000, especially about 20
000-49000.

Correspondingly, the viscosity measured at 25 ° C. in chloroform was about 0.18 to
0.7 dl / g, preferably about 0.25-0.55 dl / g, especially 0.30-0
. Limited to 50 dl / g.

The molecular weight of the polyarylene ether is generally determined by gel permeation chromatography (
A803, A804 and A containing tetrahydrofuran as eluent at room temperature
It is determined by the 805 type 0.8 × 50 cm sucrose index (TM) (Schodex ^R) separation column). A sample of this polyphenylene ether was heated at 110 ° C.
Dissolved in tetrahydrofuran under overpressure to form a solution having a concentration of 0.25% by mass.
Inject 6 ml.

Generally, detection is performed using a UV detector. The column was calibrated with a sample of polyphenylene ether whose absolute molecular weight distribution was determined by a GPC / laser light scattering combination.

Other suitable thermoplastic polymers A are polyetherimides or blends of different polyetherimides.

In principle, aliphatic or aromatic polyetherimides can be used. Polyetherimides containing both aliphatic and aromatic groups in the main chain are also suitable. For example, general formula II:

[0060]

Embedded image [However, if Q 'is, for example,

[0061]

Embedded image And Z ′ and R ′ may be independently different from each other.] May be used. For example,
Z ′ and R ′ may represent C ₁ -C ₃₀ alkylene. The alkylene group may be straight or branched, or may form a ring in close proximity. Examples of these include methylene, ethylene, n-propylene, isopropylene, cyclohexylene and n-decylene. However, Z 'and R' may represent a C ₇ -C _{3 0} alkylarylene. Examples of this include diphenylenemethane, diphenyleneethane and 2,2-diphenylenepropane. Further, Z ′ and R ′ may represent C ₆ -C ₁₈ arylene, such as phenylene or biphenylene. Each of the above-mentioned groups may be substituted by one or more substituents or may be interrupted by a heteroatom or heteroatom group. As (preferably chlorine or bromine) halogen substituents, or C ₁ -C ₁₀ alkyl (especially methyl or ethyl) is especially preferred. A heteroatom or group of heteroatoms is -S
O ₂ —, —O— and —S— are preferred. The following are some examples of suitable groups Z 'and R':

[0062]

Embedded image Wherein Q ″ represents —CyH ₂ y—, —CO—, —SO ₂ —, —O—, or —S—; q represents 0 or 1; p represents 0 or 1; Represents an integer of 1 to 5].

R ″ is C ₁ -C ₁₀ alkyl or C ₁ -C ₁₀ alkoxy, and r represents 0 or 1. Further, the polyetherimide has, in addition to the unit represented by the general formula II,
Another imide unit may be included. For example, units of the formulas II1 and II2 or mixtures thereof are suitable:

[0064]

Embedded image

Formula III:

[0066]

Embedded image [However, Z ″ and R ″ have the same meanings as Z ′ and R ′.] It is preferable to use a polyetherimide containing a repeating unit represented by the following formula:

Z ″ is

[0068]

Embedded image And R '' is

[0069]

Embedded image Particularly preferred is a polyetherimide containing a repeating unit selected from

Formula (III1):

[0071]

Embedded image A polyetherimide containing a repeating unit represented by

The polyetherimide generally has a number average molecular weight (M _n ) of 5,000 to 50,000, preferably 8,000 to 40,000. These are known or obtained in a known manner.

Accordingly, a suitable dianhydride can be reacted with a suitable diamine to obtain a polyetherimide. Generally, the reaction is carried out in the absence of a solvent or in an inert solvent at 100-250 ° C. Particularly preferred solvents are o-dichlorobenzene and m-cresol. This polyetherimide is heated at 200 to 400 ° C.
, Preferably in the melt at 230-300 ° C. In order to obtain the polyetherimide, generally, the dianhydride and the diamine are reacted in an equimolar ratio. However, a certain molar excess, for example a 0.1-5 mol% excess of dianhydride or diamine is also possible.

According to the present invention, polystyrene may be used as the polymer. Particularly preferred monomers are styrene as well as styrene having a core or side chain alkylated. Examples include chlorostyrene, α-methylstyrene, styrene, p-methylstyrene, vinyltoluene and p-tert-butylstyrene. However, it is preferred to use styrene alone.

In general, homopolymers are obtained by known bulk, solution or suspension methods (
ullmanns Enzyklopaedie der techn.Chemie, Vol. 19, pp. 265-272, Verlag Chem
ie, Weinheim 1980). The mass average molecular weight _Mw of this homopolymer is 100 to
300,000, and can be determined by a general method.

Further, the thermoplastic polymer may be a styrene-based copolymer, and according to the invention, other vinyl aromatic monomers (eg, α-methylstyrene) or substituted styrenes, such as C ₁ Copolymers based on ＣC ₁₀ alkyl styrene (eg, methyl styrene), or a mixture of different vinyl aromatic monomers, are also indicated.

For example, the styrene copolymer comprises 50 to 95% by mass, preferably 60 to 80% by mass of styrene, α-methylstyrene or substituted styrene, N-phenylmaleimide or a mixture thereof,
And preferably 5 to 50% by weight, preferably 20 to 40% by weight, of acrylonitrile, methacrylonitrile, methyl methacrylate, maleic anhydride or a mixture thereof.

The styrene copolymer is resinous, thermoplastic, and free of rubber. Particularly preferred styrene copolymer is styrene and acrylonitrile, if necessary copolymer with methyl methacrylate, α-methylstyrene and acrylonitrile, if necessary copolymer with methyl methacrylate, styrene and α-methylstyrene and acrylonitrile, If necessary, a copolymer of methyl methacrylate and a copolymer of styrene and maleic anhydride are used. A plurality of styrene copolymers described above may be used simultaneously.

These styrene copolymers are known per se and are obtained by free-radical polymerization, in particular by emulsion, suspension, solution and bulk polymerization. These viscosity numbers are about 40 to 160, corresponding to a weight average molecular weight M _w of about 4000 to 2,000,000.

A vinyl aromatic monomer such as styrene or a styrene copolymer of α-methylstyrene and a conjugated diene may be used in the novel process. A particularly preferred vinyl aromatic monomer is styrene. In particular, butadiene and isoprene are preferably used as conjugated dienes, and butadiene is preferably used. A copolymer obtained by first polymerizing a vinyl aromatic monomer and a conjugated diene and then subjecting the product to a hydrogenation reaction may be used as a styrene copolymer.

The styrene copolymer used can be obtained in particular by anionic polymerization of a vinyl aromatic monomer and a conjugated diene. Thereby, a block copolymer of these comonomers is preferentially obtained. A method for producing such a styrene copolymer is generally known (for example, US Pat. No. 3,595,942).

As the styrene copolymer, a block copolymer having a three-block structure and a branched structure having a multi-block (particularly preferable) structure, that is, a star-like structure having an arbitrary structure may be used. . The synthesis of star block copolymers obtained from vinyl aromatic monomers and diene monomers is the subject of DE-A 19 59 922, and the synthesis of star block copolymers having a large number of starting points is described in DE-A 255 50 226 and US Pat.
-The subject of A3639517.

Suitable monomers and initiators are also disclosed in the above-mentioned references. Block copolymers based on styrene as the vinyl aromatic monomer and butadiene and / or isoprene as the conjugated diene monomer are particularly preferred. The proportion of the vinyl aromatic monomer in the styrene copolymer used is generally 25 to 95% by mass, preferably 40 to 90% by mass.

Further, as thermoplastic polymer, preferably a1) a graft base comprising about 40 to 80% by weight, preferably 50 to 70% by weight, of an elastic polymer having a glass transition temperature of less than 0 ° C .; 20 to 60% by weight, preferably 30 to 50% by weight, a21) about 50 to 95% by weight, preferably 60 to 80% by weight of styrene or a substituted styrene of the above general formula III or methyl methacrylate; Or a mixture thereof, and a22) a graft layer comprising about 5 to 50% by weight, preferably 20 to 40% by weight, of acrylonitrile, methacrylonitrile, methyl methacrylate, maleic anhydride or a mixture thereof. A polymer may be used.

Suitable polymers for the graft base a1) have a glass transition temperature of less than 10 ° C., preferably less than 0 ° C., especially less than −20 ° C. Examples are natural rubber, mixtures with synthetic rubbers based on conjugated dienes or other copolymers, and elastomers based on C ₁ -C ₈ alkyl esters of acrylic acid (including other comonomers. Is also good).

The graft base a1) is preferably polybutadiene or a copolymer of butadiene and styrene.

The graft base a1) comprises: a11) at least 1% of 70 to 99.9% by weight, preferably 66 to 79% by weight.
Alkyl acrylates (alkyl groups having 1 to 8 carbon atoms), preferably n-butyl acrylate and / or 2-ethylhexyl acrylate, especially n-butyl acrylate as single alkyl acrylate A12) 0 to 30% by weight, preferably 20 to 30% by weight, of another copolymerizable monoethylenically unsaturated monomer, for example butadiene, isoprene, styrene, acrylonitrile, methyl methacrylate and / or vinyl methyl ether, and a13) from 0.1 to 5% by weight, preferably from 1 to 4% by weight, of a copolymerizable polyfunctional, preferably difunctional or trifunctional, crosslinking monomer.

Suitable difunctional or trifunctional bridging monomers a13) of this type preferably have two, optionally three or more, copolymerizable, ethylenic double bonds which are not conjugated in the 1,3-position. Is included. Examples of suitable bridging monomers are divinylbenzene, diallyl maleate, diallyl fumarate, diallyl phthalate, triallyl cyanurate and triallyl isocyanurate. The acrylate of tricyclodecenyl alcohol has been found to be a particularly effective crosslinking monomer (cf. DE-A 1 260 135).

[0089] Graft bases of this kind are known per se and have been disclosed in the literature.

The graft layer a2) is preferably such that a21) is styrene or α-methylstyrene. The monomer mixture used is particularly preferably styrene and acrylonitrile, α-methylstyrene and acrylonitrile, styrene, acrylonitrile and methyl methacrylate, styrene, N-phenylmaleimide and maleic anhydride. By graft copolymerizing the components a21) and a22), a graft layer is obtained.

The graft copolymer is a graft base a composed of a polybutadiene polymer.
If it contains 1), the term "ABS rubber" is used.

As is known per se, the graft copolymerization can be carried out in a solution, suspension or, preferably, in an emulsion. The soft phase of the graft copolymer is ABS
The average particle size (d ₅₀ value of the cumulative mass distribution) during the production of the rubber and the grafting in the emulsion is preferably 0.08 mm. For example to obtain an emulsion by coagulation or seed latex method, by increasing the particle size, 0.2 to 0.5 mm and the d ₅₀ value
Range. In such graft copolymerization, the chemical crosslinking of the polymerized monomers to the rubber to be polymerized occurs at least partially, with the crosslinking likely occurring at double bonds in the rubber. Thus, at least a portion of the monomers are grafted to the rubber, ie, covalently linked to linear rubber molecules.

The grafting may be performed in multiple stages by first grafting a portion of the monomers forming the graft shell and then grafting the rest.

The graft base a1) of the graft copolymer is composed of component a11) and, if necessary, a12
) And a13), the term "ASA" rubber is used. Its manufacture is
It is known per se and is carried out in a manner known per se.

The graft layer of the graft copolymer can be synthesized in one step or two steps.

When the graft layer is synthesized in one step, the desired mass ratio is 95: 5 to 50:50.
A mixture of the monomers a21) and a22), preferably 90:10 to 65:35, is polymerized in a manner known per se, preferably in an emulsion, in the presence of the elastomer a1).

When the graft layer a2) is synthesized in two stages, the ratio of the first stage to a2) is generally 20 to 70% by mass, preferably 25 to 50% by mass. Preferably, only monoethylenically unsaturated aromatic hydrocarbons (a21) are used for their preparation.

[0098] The ratio of the second stage of the graft layer to a2) is 30 to 80% by mass, particularly 50 to 75% by mass. The mass ratio a21) / a22) is generally 90:10 to 6
A mixture of the above-mentioned monoethylenically unsaturated aromatic hydrocarbons a21) and monoethylenically unsaturated monomers a22) of 0:40, in particular 80:20 to 70:30, is used for the preparation thereof.

The conditions for the graft copolymerization are as follows: the particle size is ₅₀ to 700 nm (d ₅₀ value of cumulative mass distribution)
Preferably, it is chosen to be Suitable means are known.

By the seed latex method, a coarse rubber distribution is obtained directly.

To obtain a very tough product, it is often advantageous to use a blend of at least two graft copolymers having different particle sizes.

For this purpose, when the particle size of the rubber is increased by a known method, for example, by agglomeration, the latex has a bimodal structure (for example, 50 to 180 nm and 200 to 700 nm).
).

Another example of the thermoplastic polymer A is an α-olefin copolymer. The α-olefin is usually a monomer having 2 to 8 carbon atoms, preferably ethylene and propylene. Alkyl acrylates or methacrylates derived from alcohols having 1 to 8 carbon atoms, preferably ethanol, butanol or ethylhexanol, and reactive comonomers such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride or glycidyl (Meth) acrylates, and also vinyl esters, especially vinyl acetate, are suitable as comonomers.
Mixtures of different comonomers may be used. Ethylene or butyl acrylate as comonomer and ethylene copolymers with acrylic acid and / or maleic anhydride are particularly suitable.

The copolymer is obtained by a high-pressure method at 400 to 4500 bar or by grafting the above comonomers onto poly-α-olefins. The amount of α-olefin in the copolymer is generally from 99.95 to 55% by mass.

[Polyamide as Thermoplastic Polymer] It is preferable to add, as a thermoplastic polymer, a polyamide obtained from a polyamide-forming monomer in two, three or four steps, particularly three or four steps of the above method. Examples of this polyamide-forming monomer include: Dicarboxylic acids such as alkanedicarboxylic acids having 6 to 12 carbon atoms, especially 6 to 10 carbon atoms, such as adipic acid, pimelic acid, suberic acid, azelaic acid or Sebacic acid, furthermore terephthalic acid and isophthalic acid; in particular diamines such as C4 to C12 alkyldiamines having 4 to 8 carbon atoms, for example hexamethyldiamine, tetramethylenediamine or octamethylenediamine, furthermore m-xylylenediamine, bis (4-aminophenyl) methane, 2
, 2-bis (4-aminophenyl) propane or bis (4-aminocyclohexyl) methane; and dicarboxylic acids and diamines, optionally in any suitable combination, but
Mixtures advantageously combined in equivalent ratios, for example hexamethylene diammonium adipate, hexamethylene diammonium terephthalate or tetramethylene diammonium adipate, preferably hexamethylene diammonium adipate, hexamethylene diammonium terephthalate.

Particular preference is given to polyamides formed from caprolactam, hexamethylenediamine and also from adipic acid, isophthalic acid and / or terephthalic acid.

The process of the present invention is in three or four steps, and adding the thermoplastic polymer to the reaction mixture in all steps of the method, but adding other polyamide-forming monomers to steps one or three. preferable. In addition, other polyamides can be added to the polymer mixture, preferably in steps 3 or 4.

In general, the total amount of monomers (polyamide-forming monomer b and aminonitrile)
30 to 100% by weight, preferably 35 to 100% by weight, of aminonitrile and 0 to 70% by weight, preferably 0 to 65% by weight, of other polyamide-forming monomers are used. 66 salt is used as an aqueous solution, and the concentration is generally 30 to
It is 75% by mass, preferably 35 to 70% by mass. Generally, aminonitrile 6
The weight ratio to the six salts is selected to be in the range of 4: 1 to 20: 1, preferably 5: 1 to 15: 1.

The thermoplastic polymer content of the reaction mixture is generally between 1 and 75% by weight with respect to the solution.
It is. Therefore, the distribution of the aminonitrile and the polyamide-forming monomer to the whole is in the range of 25 to 99% by mass. From 2 to 75% by weight, in particular from 3 to 70% by weight, of thermoplastic polymer and aminonitrile and polyamide-forming monomer in a total amount of 25%
Mixtures of up to 98% by weight, especially 30 to 97% by weight, are preferred.

According to the invention, in the first step (step 1), at least one aminonitrile and water are treated at about 90 to about 400 ° C., preferably about 180 to about 310 ° C., in particular about 22 ° C.
0 to about 270 ° C., about 0.1 to about 15 × 10 6 Pa, preferably about 1 to about 1
Heating is performed at a pressure of 0 × 10 6 Pa, especially about 4 to about 9 × 10 6 Pa. In this step, the pressure and the temperature can be mutually adjusted so as to obtain a liquid or solid phase and a mixture of the liquid or solid phase and the gas phase.

Depending on the melting point of the polyamide-forming monomer, the thermoplastic polymer may be 50-300
It is dissolved in aminonitrile and other polyamide-forming monomers at a temperature in the range of 0 ° C, preferably in the range of 80 to 190 ° C. In order to thoroughly mix the components of this solution, it is effective to stir the mixture. For this purpose, for example, stirred tanks are suitable. In general, the water is then added at the same time in small portions or continuously. The temperature of the solution
Simultaneously or subsequently, the temperature is raised to 180-330 ° C, preferably to 220-330 ° C. This solution may be left in the apparatus from which it is obtained, or may be transferred to a separate reaction vessel before or after heating or before or after addition of water, especially in the case of a continuous reaction.

According to the invention, water is present in a molar ratio of aminoalkyl to water of from 1: 1 to 1:
30 range, particularly preferably from 1: 2 to 1: 8, very preferably from 1: 2 to 1: 6.
It is preferred to use water in excess of the aminoalkyl nitrile used.

In this embodiment, the liquid phase or the solid phase or a mixture of the liquid phase and the solid phase corresponds to the reaction mixture, but the gas phase is separated and removed. As part of this step, the gas phase, the liquid phase or the solid phase, or a mixture of the solid phase and the liquid phase may be separated once, or the synthetic mixture formed in this step may be in a two-phase form, ie, , Liquid phase / gas phase, solid phase / gas phase or (liquid-solid) phase / gas phase. Of course, the pressure and the temperature can be mutually adjusted so that the synthesis mixture exists as a single solid or liquid phase.

The removal of the gas phase can be carried out using a separation tank or a group of tanks with or without a stirrer and with evaporators, such as circulatory evaporators or thin-layer evaporators (eg film extrusion) Or an annular disk reactor which ensures an increased phase interface. Recycling of the synthesis mixture or use of a loop reactor may be necessary to increase the phase interface. Further, the addition of water vapor or an inert gas to the gas phase can promote removal of the gas phase.

Preferably, the pressure is adjusted at a preselected temperature to be less than the equilibrium vapor pressure of ammonia, but greater than the equilibrium vapor pressure of the other components of the synthesis mixture at a given temperature. This can particularly assist in the removal of ammonia, thereby increasing the rate of hydrolysis of the acid amide group.

The two-phase process is preferably carried out at a pressure greater than the vapor pressure of pure water according to the temperature of the reaction mixture, but less than the equilibrium vapor pressure of ammonia.

Step 1 can be performed in a tank with a stirrer, a fluidized tube or a group of tanks. The two-phase method is preferably performed using a tank or a reaction column, but when a single liquid phase is involved, it is preferably performed using a packed flow tube. The use of a selectively packed tube bundle reactor in the first process step is also possible in a two-phase process, in particular to improve the heat transfer and further reduce the axial backmixing of the reactants. , Is also effective.

In order to ensure a narrow residence time distribution and to limit the backmixing, useable filling elements are, for example, Raschig rings or Sulzer mixing elements.

In another embodiment, the reactor of the first step is operated in a downward flow regime, where it is preferred to additionally have a filling element which limits any back mixing of the reactants. As a result, after preferentially direct introduction into the reactor, the ammonia gas liberated in the reactor reaches the gas phase at the top of the reactor by the closest route. Thus, disturbances due to flow distribution in other paths of the reactor due to bubble rise or convection are minimized.

In a particularly preferred embodiment of the two-phase process, a rigid flow tube with another opening for gas phase removal on the product outlet is operated in upward flow. The tubular reactor can be partially or completely filled with catalyst particles. In a preferred embodiment, the rigid reactor used in the two-phase process is filled to the maximum with the catalytic material to the phase boundaries.

In another particularly preferred embodiment of the first step, the reaction mixture is as a single liquid phase,
That is, the pressure is selected such that there is no gas phase in the reactor. In this single-phase method,
A preferred embodiment is a flow tube filled only with the catalyst material.

In another preferred embodiment, the aminonitrile / water mixture is continuously heated using a heat exchanger, so that the heated mixture is heated to the same temperature with the thermoplastic polymer and the polyamide-forming monomer. Internal filling, preferably a Sulzer mixing element, if necessary to avoid back mixing
Into a tube that may contain Of course, the aminonitrile / water mixture can be heated separately from the thermoplastic polymer and other monomers and then mixed in the reactor.

The residence time of the synthesis mixture in the first step is not particularly limited, but is generally set in the range of about 10 minutes to about 10 hours, preferably in the range of about 10 minutes to about 6 hours.

The degree of conversion of the nitrile group in step 1 is not limited, but the conversion of the nitrile group in step 1 is at least about 70 mol%, preferably at least at least 70 mol%, based on the number of moles of aminonitrile used. More than about 95 mole%, especially in the range of about 97 to about 99 mole%, is particularly required for economic reasons.

The conversion of the nitrile groups is usually measured by IR spectroscopy (CN stretching vibration at wave number 2247), Raman spectroscopy, NMR or HPLC, preferably IR spectroscopy.

The present invention relates to the reaction of step 1 (and other steps, particularly step 2 and / or step 3)
Oxygen-containing phosphorus compounds, especially phosphoric acid, phosphorous acid and hypophosphorous acid, and their alkali metal salts, alkaline earth metal salts and ammonium salts (for example, Na3PO4
, NaH2PO4, Na2HPO4, NaH2PO3, Na2HPO3, NaH
2PO2, K3PO4, KH2PO4, K2HPO4, KH2PO3, K2HP
O3, KH2PO2) is not excluded, in which case the molar ratio of ω-aminonitrile to phosphorus compound is from 0.01: 1 to 1: 1.
, Preferably in the range of 0.01: 1 to 0.1: 1. Further, a catalyst described below can be used.

The reaction of Step 1 is performed by using a β-zeolite catalyst, a plate-like silicate catalyst,
It can be carried out in a fluid tube containing a Bronsted acid catalyst containing 0% by mass of anatase and 0 to 30% by mass of rutile, and up to 40% by mass of which may be replaced by a titanium dioxide catalyst which may be replaced by tungsten oxide. . When using high-purity aminonitrile, the proportion of anatase in the titanium dioxide should be as high as possible. Preferably, a pure anatase catalyst is used. When the aminonitrile used contains, for example, 1 to 3% by mass of impurities, it is preferable to use a titanium dioxide catalyst containing a mixture of anatase and rutile. 70 to 8 of anatase
It is preferable that the proportion of rutile is 0 to 30% by mass. In this case, it is particularly preferred to use a titanium dioxide catalyst consisting of about 70% by weight of anatase and about 30% by weight of rutile. The pore volume of this catalyst is between 0.1 and 5 ml / g, in particular
. It is preferably between 2 and 0.5 ml / g. Average particle size is 0.005-0.1m
m, particularly preferably in the range of 0.01 to 0.06 mm. If a highly viscous product is used, its average particle size should be large. Cutting hardness
hardness) is preferably more than 20N, especially more than 25N. BET surface area is 4
It is preferably greater than 0 m2 / g, especially greater than 100 m2 / g. If the BET surface area is less than the above, the column bed volume should be appropriately high to ensure adequate catalytic activity. The catalyst is particularly preferably of the following properties:
100% anatase; pore volume of 0.3 ml / g; average particle size of 0.02 mm;
32N cut hardness; 116 m2 / g BET surface area or 84% by weight anatase; 16% by weight rutile; 0.3 ml / g pore volume; average particle size of 0.03 mm;
Cutting hardness of 26N; BET surface area of 46 m2 / g. This catalyst is, for example, degussa (
Degussa), Finnti or commercially available powders such as those obtained by Kemira. If tungsten oxide is used, up to 40% by weight, preferably up to 30% by weight, particularly preferably up to 15 to 25% by weight, of titanium dioxide may be replaced by tungsten oxide. This catalyst is transferred to Ertl,
Knoezinger, Weitkamp: "Handbook of heterogeneous catalysis", VHC Weinhei
m, 1997, pp. 98 et seq. The catalyst can be used in any desired form. It is preferably used in the form of shaped bodies, extrudates, granules, coated fillings or filling contents, in particular in the form of granules. The granules are
Preferably large enough to allow easy separation from the product mixture,
Does not impair product flow during the reaction.

By making the catalyst into a granular form, it can be mechanically removed at the outlet of the first step. For this purpose, for example, a mechanical filter or sieve is provided at the outlet of the first step. If the catalyst is used further in the second and / or third step, it is preferably used in a similar form.

According to the invention, the reaction mixture obtained in the first step is treated in a second step in about 200 (
150) to about 350 (400) ° C., preferably about 210 (200) to about 3
The reaction is further carried out at a temperature in the range of 00 (330) ° C., especially in the range of about 230 (230) to 270 (290) ° C., at a pressure lower than the pressure in step 1. The pressure in the second step is preferably at least about 0.5 × 10 6 Pa lower than the pressure in step 1 and generally ranges from about 0.1 to about 45 × 10 6 Pa, preferably from about 0.5 to about 15 × 10 5 Pa.
The range is 6 Pa, in particular, about 2 to about 6 × 10 6 Pa (insertion value: when no catalyst is used).

In step 2, the temperature and pressure are reduced to obtain a first gas phase and a first liquid phase or a first solid phase, or a mixture of the first liquid phase and the first solid phase, and It is selected to separate the first gas phase from the first liquid phase or the first solid phase, or a mixture of the first liquid phase and the first solid phase.

The first gas phase consisting essentially of ammonia and water vapor is continuously removed using a distillation apparatus, for example a distillation column. The organic component of the distillate that is co-removed during this distillation, preferentially unreacted aminonitrile, can be wholly or partially recycled to step 1 and / or step 2.

The residence time of the reaction mixture in Step 2 is not limited, but generally ranges from about 10 minutes to about 5 hours, preferably from about 30 minutes to about 3 hours. It is.

The production line between the first and second steps may include a filling element, for example a Raschig ring or a Sulzer mixing element, which facilitates the controlled expansion of the reaction mixture into the gas phase. This is used in particular for the single-phase method.

If desired, the reaction mixture of the first step may further be metered with further thermoplastic polymer and / or polyamide-forming monomers into the first step, preferably continuously and into the liquid phase.

The reactor of the second step may contain the catalyst material of the present invention, particularly in granular form.
Compared to a reactor without a catalyst, this reactor allows, in particular, at relatively high pressures and / or
Alternatively, it has been found that the physical properties of the product are further improved when the amount of water in the reaction mixture is excessively large. The temperature and pressure are chosen so that the viscosity of the reaction mixture is kept sufficiently low that the surface of the catalyst does not become clogged. According to the invention, the outlet of the second treatment step is also provided with a sieve or filter for ensuring the purity of the reaction mixture and separating the catalyst and the reaction mixture.

In step 3, the first liquid phase or the first solid phase, or a mixture of the first liquid phase and the first solid phase, is mixed with a gas phase or a liquid phase containing an aqueous medium, preferably with water or Steam and
About 90 to about 400 ° C, preferably about 180 to 310 ° C, especially about 220 to about 270
° C., about 0.1 to about 15 × 10 6 Pa, preferably about 1 to 10 × 10 6 Pa
In particular, mixing is performed under conditions of a pressure of about 4 to 9 × 10 6 Pa. This is preferably done continuously. The amount of water (as a liquid) to be added is preferably about 5 kg per 1 kg of the first liquid phase or the first solid phase, or a mixture of the first liquid phase and the first solid phase.
The range is from 0 to about 1500 ml, more preferably from about 100 to about 500 ml, but no thermoplastic polymer is added. The addition of water offsets the loss of water received in step 2 and promotes the hydrolysis of the acid amide groups of the synthesis mixture. This provides a further advantage of the present invention, i.e. a mixture of starting materials as used in step 1 can be used with only a slight excess of water.

When not only water but also a thermoplastic polymer and a polyamide-forming monomer are added to step 3, the amount of water added depends on the solubility in water and the amount of thermoplastic polymer added. Depending on the melting points of the components used, the thermoplastic polymers and monomers are converted into the liquid phase and brought to the required temperature and, if necessary, mixed with water. In order to complete the mixing, it is effective to stir the mixture. For example, a stirred tank is suitable for this. Thereafter, the solution is brought to the reaction temperature required in the third treatment step and mixed with the first liquid phase or the first solid phase, or a mixture of the first solid phase and the first liquid phase. For this purpose, the reactor may be provided with a mixing element for promoting the mixing of the components.

Step 3 can be performed under the conditions of a temperature of 150 to 370 ° C. and a pressure of 0.1 to 30 × 10 6 Pa. If a catalyst bed according to the invention is present, the conditions of step 1 may be adapted. Otherwise, the temperature is 180-300 ° C, especially 220-
Preferably it is 280 ° C. The pressure is 1 to 10 × 10 6 Pa, especially 2 × 10 6 Pa
The pressure is preferably set to 7 × 10 6 Pa.

The temperature and the pressure can be mutually adjusted so that the synthesis mixture is present as a single liquid or solid phase. In another embodiment, the pressure and temperature are selected so as to obtain a liquid or solid phase, or a mixture of solid and liquid phases, and even a gas phase. In this embodiment, the liquid or solid phase or the mixture of the liquid and solid phases corresponds to the product mixture, but the gas phase is separated off. As part of this step, the gas phase can be separated once from a liquid or solid phase, or a mixture of solid and liquid phases, or the synthetic mixture formed during this step can be converted to a two-phase form Ie, liquid / gas, solid / gas or liquid-solid / gas.

The pressure can be adjusted at a preselected temperature to be below the equilibrium vapor pressure of ammonia, but above the equilibrium vapor pressure of the other components in the synthesis mixture at a given temperature. In this way, the hydrolysis of the acid amide group can be accelerated, especially since the removal of ammonia can be assisted.

The equipment / reactor that can be used in this step may be the same as in step 1, as described above.

The residence time of this step is likewise not particularly limited, but for economic reasons generally ranges from about 10 minutes to about 10 hours, preferably from about 60 minutes to about 8 hours, especially about 60 minutes. It is required to be in the range of minutes to about 6 hours.

The product mixture obtained in step 3 can be further obtained as follows.

In a preferred embodiment, the product mixture of Step 3 is combined in a fourth step with about 200 to about 3
The post-condensation is carried out at a temperature of 50 ° C, preferably about 220-300 ° C, especially about 240-270 ° C. Step 4 is performed at a lower pressure than step 3, preferably about 5-100
The range is 0 × 103 Pa, and more preferably the range is about 10 to about 300 × 103 Pa. In connection with this step, the temperature and the pressure are the second gas phase and the second liquid phase or the solid phase, or the mixture of the second liquid phase and the second solid phase, wherein each said phase is a polyamide. Is included).

According to the invention, the reaction of the reaction mixture according to the fourth step can also be carried out in the presence of a newly added thermoplastic polymer. Depending on the melting point, the thermoplastic polymer is transferred to the liquid phase at a temperature in the range from 50 to 300C, preferably in the range from 80 to 290C. As a feed tank, for example, a stirred tank is suitable here. The solution is then heated to the reaction temperature required in the fourth treatment step and mixed with the liquid or solid phase, or the mixture of solid and liquid phases, which is the reaction effluent from the third or second reaction step. Mixing elements may be used to facilitate mixing of the components. In another preferred embodiment, the liquid or solid thermoplastic polymer is introduced separately from the product output of the third step into the reactor of the fourth step, where it is mixed, for example using a stirrer.

The post-condensation of step 4 results in a relative viscosity of the polyamide (measured at a temperature of 25 ° C., at a concentration of 1 g of polymer per 100 ml of 96% strength by weight sulfuric acid) in the range from about 1.6 to about 3.5. It is preferably performed to obtain a value.

[0147] In a preferred embodiment, the liquid water can be drained using an inert gas such as nitrogen.

The residence time of the reaction mixture of step 4 varies depending, inter alia, on the desired relative viscosity, temperature, pressure and the amount of water added in step 3.

If step 3 is carried out in a single-phase process, the production line between steps 3 and 4 is filled, which allows for controlled expansion of the synthetic mixture in the gas phase, for example a Raschig ring or a Sulzer mixing element. An element may be included.

The fourth step may be performed using the catalyst of the present invention. By using this catalyst in process step 4, especially in the case of the third or third step process-the relative viscosity of the effluent from the second step is less than RV = 1.6 and / or used If the molar content of nitrile groups and acid amides in the polymer, based on the number of moles of aminonitrile, exceeds 1%, the molecular weight construction will be improved.

In a further preferred embodiment of the invention, without step 3, the production of the polyamide can be carried out according to steps (1), (2) and (4).

The method described above, ie steps (1) to (3) according to the invention, or (1), (2)
And each sequence of (4) or (1) to (4) can be performed in a batch process, ie, continuously in a single reactor, or in a continuous process, ie, simultaneously in a continuous reactor. .
Of course, some of these steps, for example steps (1) and (2), may be performed in a continuous manner and the remaining steps in a batch manner.

In a further preferred embodiment of the present invention, at least one of the gas phases obtained in each step can be reused in at least one of the preceding steps.

The temperature and pressure of Step 1 or Step 3, or both Step 1 and Step 3, are adjusted to a liquid or solid phase, or a mixture of liquid and solid phases and a gas phase, and the gas phase is separated. More preferably, it is selected to be removed.

According to the invention, all steps in which the polymer is present should be carried out with thorough mixing of the polymer with the reserved monomer. In particular, in Steps 2 and 4, it is particularly preferable to use a device such as a stirrer that ensures a clear shearing of the reaction mixture.

In addition, chain extension or branching, or a combination thereof, can be performed with the methods of the present invention. For this purpose, polymer branching or chain-extending substances known to the person skilled in the art are added in individual steps. These materials are used in Step 3
Alternatively, it is preferably added in step 4.

The substances which can be used are: Branching or crosslinking agents include trifunctional amines or carboxylic acids. Suitable examples of at least trifunctional amines or carboxylic acids are described in EP-A0345.
648. The at least trifunctional amine contains at least three amino groups that can react with a carboxylic acid group. These preferably do not contain carboxylic acid groups. The at least trifunctional carboxylic acid contains at least three carboxylic acid groups that can react with the amine and can also be present in the form of derivatives thereof such as, for example, esters. Preferably, the carboxylic acid does not contain an amino group that can react with a carboxylic acid group. Examples of suitable carboxylic acids include trimesic acid, trimerized fatty acids derived from oleic acid and having 50 to 60 carbon atoms, naphthalene polycarboxylic acids (eg, naphthalene-1,3,5,7-tetracarboxylic acid) Is mentioned. The carboxylic acid is preferably a defined compound and not a high molecular compound.

Examples of amines having at least three amino groups include nitrotrialkylamines (especially nitrilotrietanamines), dialkylenetriamines (especially
Diethylenetriamine), trialkylenetetraamine and tetraalkylenepentaamine, wherein the alkylene moiety is preferably an ethylene unit. In addition, dendrimers can be used as amines. Dendrimers have the general formula I:

[0159]

Embedded image Wherein R represents H or-(CH2) n-NR12, R1 represents H or-(CH2) n-NR22, R2 represents H or-(CH2) n-NR32, and R3 represents H or-(CH2) n-NH2, wherein n is an integer from 2 to 6 and x is an integer from 2 to 14].

N is 3 or 4, especially 3, and x is an integer from 2 to 6, preferably 2 to 4, especially 2. The radicals R may, independently of one another, have the meaning given above. R is preferably a hydrogen atom or a group-(CH2) n-NH2.

Suitable carboxylic acids are those having a carboxylic acid group having 3 to 10 carbon atoms, preferably 3 or 4 carbon atoms. Carboxylic acids having an aromatic nucleus and / or a heterocyclic nucleus are preferred. Examples include benzyl, naphthyl, anthracene, biphenyl, triphenyl groups, or heterocycles such as pyridine, bipyridine, pyrrole, indole, furan, thiophene, purine, quinoline, phenanthrene, porphyrin, phthalocyanine, and naphthalocyanine. 3,5,3 ′, 5′-biphenyltetracarboxylic acid, phthalocyanine, naphthalocyanine, 3,5,5 ′, 5′-biphenyltetracarboxylic acid, 1,3,5,7-naphthalenetetracarboxylic acid, 2,
4,6-pyridinetricarboxylic acid, 3,5,3 ′, 5′-bipyridyltetracarboxylic acid, 3,5,3 ′, 5′-benzophenonetetracarboxylic acid, 1,3,6
8-Acridinetetracarboxylic acid is preferable, and 1,3,5-benzenetricarboxylic acid (trimesic acid) and 1,2,4,5-benzenetetracarboxylic acid are particularly preferable. Such compounds are commercially available or described in DE-A 431 218.
2 can be obtained. When using ortho-substituted aromatic compounds, imide formation is preferably prevented by appropriately selecting the reaction temperature.

These substances are at least trifunctional, preferably at least tetrafunctional. The number of functional groups is 3 to 16, preferably 4 to 10, especially 4 to 8. The process of the present invention is carried out with at least a trifunctional amine or at least a trifunctional carboxylic acid, but no mixture of such amines or carboxylic acids is used.
However, a small amount of at least trifunctional amine may be present in the trifunctional carboxylic acid and vice versa.

The above substances are used in an amount of 1 to 50 mmol / g, preferably 1 to 35 mmol / g, based on polyamide.
It is preferably present in an amount of mmol / g, especially 1-20 mmol / g. This material is used in an amount of 3 to 150 equivalents of mmol / g, preferably 5 to 1 equivalent to the polyamide.
It is preferably present in an amount of 00 equivalents mmol / g, especially 10-70 equivalents mmol / g. This equivalent is based on the number of functional amino or carboxylic acid groups.

A bifunctional carboxylic acid or a bifunctional amine is used as a chain extender. These contain two carboxylic acids capable of reacting with an amino group, or two amino groups capable of reacting with a carboxylic acid. A bifunctional carboxylic acid or amine does not contain a carboxylic acid group or an amino group, as well as any other functional group capable of reacting with an amino group or a carboxylic acid group. They preferably do not contain any other functional groups. Examples of suitable bifunctional amines are those which form salts with bifunctional carboxylic acids. These are linear aliphatics such as C1-14 alkylenediamines, preferably C2-6 alkylenediamines (eg, hexylenediamine). These may also be alicyclic. For example, isophorone diamine, dicycycan, laromine can be mentioned. Branched aliphatic diamines can likewise be used, for example Vestamin TMD (trimethylhexamethylenediamine, manufactured by Huels AG). Further, they may be diamines. All amines are each C1-12 alkyl, preferably C1-1.
It may be substituted on the carbon skeleton with a 4-alkyl group.

The bifunctional carboxylic acid forms a salt with a bifunctional diamine, for example. These are linear aliphatic dicarboxylic acids, preferably C4-20 dicarboxylic acids. For example, adipic acid, azelaic acid, sebacic acid, suberic acid may be mentioned. These may be aromatic. Examples include isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, and dimerized fatty acids.

It is preferred to use the bifunctional base building block in an amount of 1 to 55 mmol / g, more preferably 1 to 30 mmol / g, especially 1 to 15 mmol / g, based on the polyamide.

According to the invention, the product mixture obtained in step 3 or the second liquid phase or the second solid phase or a mixture of the second liquid phase and the second solid phase (from step 4) (each The polyamide, preferably comprising the molten polymer, is discharged from the reaction vessel in a conventional manner, for example by a pump. Subsequently, the obtained polyamide was subjected to DE-A 43 16 683
(Page 3, line 54 to page 4, line 3) can be post-processed in a conventional manner as described in detail.

In a preferred embodiment, the level of cyclic dimer in nylon-6 obtained according to the invention is such that the polyamide is first extracted with an aqueous solution of caprolactam, then with water and / or by gas-phase extraction (EP-A 0284968). ) Can be further reduced. The low molecular weight components, such as caprolactam, chain caprolactam oligomer and cyclic caprolactam oligomer, obtained in this post-treatment can be reused in the first and / or second and / or third step.

The mixtures of the starting materials and the synthesis mixtures are used in all steps with chain regulators (for example aliphatic and aromatic carboxylic and dicarboxylic acids) and catalysts (for example acid-containing phosphorus compounds). The polyamide-forming monomer and the aminonitrile can be mixed in an amount of 0.01 to 5% by mass, preferably 0.2 to 3% by mass based on the amount of the aminonitrile. Suitable chain regulators include, for example, propionic acid, acetic acid, benzoic acid, terephthalic acid and triacetone diamide.

Additives and fillers (eg, pigments, dyes and stabilizers) are generally added to the synthesis mixture before pelletization, preferably in the second, third and fourth steps. Whenever the synthetic or polymer mixture does not encounter a fixed bed catalyst during subsequent processing,
It is particularly preferred to use fillers and additives. One or more impact rubbers can be present as additives in the composition in an amount of 0 to 40% by weight, preferably 1 to 30% by weight, based on the total composition.

For example, it is possible to use customary impact modifiers suitable for polyamides and / or polyarylene ethers.

[0172] Rubbers that increase the toughness of polyamides generally have two essential characteristics: they have an elastic part with a glass transition temperature of less than -10 ° C, preferably less than -30 ° C, and interact with the polyamide. It contains at least one possible functional group. Suitable functional groups include, for example, carboxylic acids, carboxylic anhydrides, carboxylic esters, carboxylic amides, carboxylic imides, amino, hydroxyl, epoxide, urethane and oxazoline groups.

Rubbers that increase the toughness of the blend include: EP and EPDM rubbers grafted with the above functional groups. Suitable grafting agents include, for example, maleic anhydride, itaconic acid, acrylic acid, glycidyl acrylate and glycidyl methacrylate.

These monomers can be used in the molten or solution state in free radical initiators (eg,
The polymer can be grafted in the presence or absence of (cumene hydroperoxide).

Copolymers of the α-olefins described above for the polymers, in particular including ethylene copolymers, can be used as rubbers instead of polymer A and can be used as such (copolymer) in the compositions of the invention. (Combined).

Another suitable class of elastomers are core-shell graft rubbers. They are,
A graft rubber produced in an emulsion and containing at least one hard component and one soft component. The hard component is typically a polymer having a glass transition temperature of at least 25 ° C, while the soft component is a polymer having a glass transition temperature of 0 ° C or less. The structure of these products consists of a core and at least one shell, the structure being obtained in the order in which the monomers are added. The soft component is generally derived from butadiene, isoprene, alkyl acrylate, alkyl methacrylate or siloxane and optionally another comonomer. Suitable siloxane cores can be prepared, for example, starting from the cyclic oligomer octamethyltetrasiloxane or tetravinyltetramethyltetrasiloxane. These can be reacted with, for example, γ-mercaptopropylmethyldimethoxysilane in a ring-opening cationic polymerization, preferably in the presence of sulfuric acid, to form a soft siloxane core. The siloxane may be crosslinked by a polymerization reaction in the presence of a silane having a hydrolyzable group such as a halogen or an alkoxy group (for example, tetraethoxysilane, methyltrimethoxysilane or phenyltrimethoxysilane). good. Suitable comonomers include, for example, styrene, acrylonitrile, and bridging or grafting monomers containing one or more polymerizable double bonds (eg, diallyl phthalate, divinylbenzene, butanediol diacrylate or triallyl (iso) cyanurate). Can be The hard component is generally derived from styrene, α-methylstyrene and copolymers thereof, and acrylonitrile,
Methacrylonitrile and methyl methacrylate are preferred.

Preferred core-shell graft rubbers have a soft core and a hard shell, or a hard core, a first soft shell and at least one other hard shell. The introduction of functional groups such as carbonyl, carboxylic acid, acid anhydride, acid amide, acid imide, carboxylic acid ester, amino, hydroxyl, epoxy, oxazoline, urethane, urea, lactam or halobenzyl is here referred to as the last shell The polymerization is preferably carried out by adding a suitably functionalized monomer during the polymerization. Suitable functionalized monomers include, for example, maleic acid, maleic anhydride, mono- or diesters of maleic acid, tert-butyl (meth) acrylate, acrylic acid, glycidyl (meth)
Acrylates and vinyl oxazolines. The proportion of the monomer containing a functional group is generally 0.1 to 25% by mass based on the total mass of the core-shell graft rubber.
, Preferably in the range of 0.25 to 15% by mass. The mass ratio of the soft component to the hard component is generally in the range from 1: 9 to 9: 1, preferably in the range from 3: 7 to 8: 2.

Such rubbers which increase the toughness of polyamides are known per se, for example E
It is disclosed in P-A0208187.

Another suitable impact modifier is a thermoplastic polyester elastomer. Polyester elastomers are segmented copolymerized polyetheresters that include long chain segments (generally derived from poly (alkylene) ether glycol) and short chain segments (derived from low molecular weight diols and dicarboxylic acids). Such products are known per se and are described in the literature, for example in US Pat.
14. The corresponding products are commercially available under the trade names Hytrel® (Du Pont), Arnitel® (Akzo) and Pelprene® (Toyobo Co. Ltd.).

It is also possible and suitable to use mixtures of different rubbers.

As other additives, for example, processing aids, stabilizers and oxidation inhibitors, thermal decomposition inhibitors and UV decomposition inhibitors, lubricants and molded product removal agents (mold release agents), flame retardants, dyes and pigments, And a plasticizer is mentioned. The proportion is generally up to 40% by weight, preferably up to 15% by weight, based on the total weight of the composition.

The pigments and dyes are generally present in an amount of up to 4% by weight, preferably 0.5 to 3.5% by weight, particularly preferably 0.5 to 3% by weight.

Pigments for colored thermoplastics are generally known and are described, for example, in R. Gaechter.
and H. Mueller, Taschenbuch der Kunststoffadditive, Carl Hanser Verlag,
1983, pp. 494-510. The first preferred types of pigments described include zinc oxide, zinc sulfide, lead white (2PbCO3.Pb (OH) 2), lithopone,
White pigments such as antimony white and titanium dioxide. With respect to the two mostly common polymorphs of titanium dioxide (rutile and anatase), the rutile form is preferred for use as a white pigment for the molding compositions of the present invention.

The black pigments that can be used according to the invention include iron oxide black (Fe3O4), spinel black (Cu (Cr, Fe) 2O4), manganese black (mixture of manganese dioxide, silicon dioxide and iron oxide), cobalt Black and antimony black, especially carbon black commonly used in the form of furnace black or gas black (G. Benzing, Pigmente fuer Anstrichmittel, Expert-Verla
g (1988), p. 78 et seq.).

A specific hue is obtained according to the invention using inorganic coloring pigments, for example chromium oxide green, or organic coloring pigments, for example azo pigments and phthalocyanines. Such pigments are generally commercially available.

Furthermore, it is effective to use a mixture of the above-mentioned pigments or dyes, for example, a mixture of carbon black and copper phthalocyanine. This is because, in general,
It is conceivable to facilitate the color dispersion of the thermoplastic.

The oxidation inhibitor and the heat stabilizer that can be added to the thermoplastic composition of the present invention include, for example, halides of metals of Group I of the periodic table (eg, sodium halide, potassium halide, lithium halide) ) And optionally used together with copper (I) halide (for example, chloride, bromide or iodide). In particular, the copper halide may further include an electron-rich p-ligand. Examples of such copper complexes include copper halide complexes with triphenylphosphine. In addition, zinc fluoride and zinc chloride can be used. Alternatively, sterically hindered phenols, hydroquinones, substituted representatives of this group, secondary aromatic amines, optionally in combination with phosphorus-containing acids and their salts, and mixtures of these compounds, preferably mixtures At a concentration of up to 1% by weight with respect to the weight of

Examples of UV stabilizers include various substituted resorcinols, salicylates, benzotriazoles and benzophenones, which are generally used in amounts of up to 2% by weight.

[0189] Lubricants and demolding agents which are generally contained in the thermoplastic material in amounts of up to 1% by weight include stearic acid, stearyl alcohol, alkyl stearate and N-alkylstearamide, And esters of pentaerythritol with long-chain fatty acids. Calcium, zinc or aluminum salts of stearic acid and dialkyl ketones (eg, distearyl ketone) can also be used.

The present invention further provides a polyamide produced by any of the methods described above.

[0191] Mixtures of polyamides (especially nylon-6) and their copolymers, and thermoplastic polymers can be used in the production of fibers, films and moldings.

The advantage of the process of the invention during processing is, in particular, that the chain length of the thermoplastic polymer is minimized anyway and that the polymer is present in the composition in a very finely dispersed state. Furthermore, aminonitrile can be used in the production of nylon-6 according to the invention.

[0193] Another advantage is that the inherent color of the composition obtained by the method of the present invention is pale.

The following examples illustrate the invention.

[0195]

【Example】

Sample preparation and analysis Relative viscosity (RV), built-up molecular weight measurement and degree of polymerization, 1% by weight for extracted material and 1.1% by weight for unextracted polymer, respectively 9
It was measured at 25 ° C. in a 6% strength sulfuric acid solution using an Ubbelohde viscometer. The unextracted polymer was dried for 20 minutes under reduced pressure before analysis.

The content of amino and carboxyl end groups (AEG and CEG, respectively) was
It was determined by acid titration based on the extracted polycaprolactam. Amino groups were titrated with perchloric acid dissolved in 70:30 (parts by mass) phenol / methanol as solvent. The carboxyl end groups were titrated with a potassium hydroxide solution dissolved in benzyl alcohol as a solvent.

For extraction, 100 parts by weight of polycaprolactam were stirred with 400 parts by weight of demineralized water at 100 ° C. under reflux for 32 hours, water was removed and then gradually at 100 ° C. under reduced pressure for 20 hours. Dry, ie without post-condensation.

All of these experiments were performed on a multi-stage processor. In the first stage, the empty volume is 1
L (liters) and an internal height of 1000 mm, completely filled with Raschig ring filling elements (3 mm diameter, 3 mm length) or granules of titanium dioxide. The granules (Type S from Finty) are 100% TiO2 in anatase form,
The strand length was in the range of 2 to 14 mm, the strand thickness was about 4 mm, and the specific surface area was more than 100 m2 / g. As a second step, a 2 L separation tank was used. The third stage was a Raschig ring (diameter 6 mm, length 6 mm) or a flow tube (volume 1 L, length 1000 mm) filled with the TiO2 granules described above.
The fourth stage was a separation tank (2 L capacity) in which the produced molten polymer was removed in a strand by a gear pump.

The processing equipment was operated in both stages 1, 2 and 4 (Examples 4, 5 and 6) and stages 1, 2, 3 and 4 (Examples 1, 2 and 3). The thermoplastic polymer was introduced into the reaction mixture before the fourth stage. Comparative products or experiments were obtained by preparing polymers from ACN under the same processing conditions or with the same processing parameters without this thermoplastic polymer.

[Tables of Examples] Processing parameters and physical properties of products are shown in the following table. The throughput is the mass flow rate of the reaction mixture after the first processing stage.

[Thermoplastic Polymer Used] PS: a polyarylene ether sulfone containing a repeating unit represented by the formula I2 and having a viscosity number of 48 ml / g, for example, Ultrason S 1010 (manufactured by BASF).

SAN: poly (styrene-co-acrylonitrile) with an acrylonitrile content of 25% by weight and a viscosity number (measured at 25 ° C. with a 0.5% strength by weight solution in dimethylformamide at 25 ° C.) .

[0203]

[Table 1]

Comparative Results The viscosities of the products are recorded in the melt by vibrating shear and in sulfuric acid as solvent by means of a capillary viscometer. Amino end group (AEG) content and carboxyl end group (C
The polymer blend was further analyzed for EG) content. The purity of aminocapronitrile was 99.5%.

[0205]

[Table 2]

[Procedural Amendment] Submission of translation of Article 34 Amendment of the Patent Cooperation Treaty

[Submission date] March 17, 2000 (2000.3.17)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

──────────────────────────────────────────────────の Continuation of front page (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE ), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, AU, BG, BR, BY, CA, CN, CZ, GE, HU, ID, IL, IN, JP , KR, KZ, LT, LV, MX, NO, NZ, PL, RO, RU, SG, SI, SK, TR, UA, US (72) Inventor Hildebrand, Folker Germany, D-68169, Mannheim, Am, Brunnengarten, 23F term (reference) 4J001 DA01 DB01 EA06 EB06 EB07 EB08 EB09 EB14 EB36 EB37 EC07 EC08 EC09 EE04D EE08D EE18D EE56A FA 03 FB03 FB05 FC03 FC05 GA13 GB02 GB03 GB04 JA01 JA10 JA12 JC01 4J002 BB04W BC03W BC04W BN07W BN15W CH06W CH07W CL00W CL03X CM04W CN03W ET006 FD016

Claims (11)

[Claims] 1. A process for producing a polymer blend by reacting at least one amino nitrile with water in the presence of a thermoplastic polymer and optionally other polyamide-forming monomers, comprising: (1) 90-400 ° C. Reacting at least one kind of aminonitrile with water at a temperature of 0.1 to 35 × 10 ⁶ Pa to obtain a reaction mixture; and (2) further adding 150 to 400 to the reaction mixture. C., at a pressure lower than that in step (1), wherein the temperature and the pressure are changed to a first gas phase and a first liquid phase or a first solid phase, or a first solid phase. And a mixture of the first liquid phase is obtained, and the first gas phase is formed from the first liquid phase, the first solid phase, or the first liquid phase and the first solid phase. Separating from the mixture; and (3) the first liquid phase or the first liquid phase. Solid phase or mixture of first liquid and first solid phase, mixed with the gas phase or liquid phase comprising water at a pressure at a temperature of 150~370 ℃, 0.1~30 × 10 ⁶ Pa of Producing a polymer blend by adding the thermoplastic polymer and, if necessary, other polyamide-forming monomers in one or more of the steps. 2. The following steps: (4) the polymer blend is post-condensed at a temperature of 200 to 350 ° C. and a lower pressure than in step (3), wherein the temperature and pressure are Water- and ammonia-containing gas phase and secondary
3. The method of claim 1, comprising selecting to obtain a liquid phase or a second solid phase, or a mixture of a second liquid phase and a second solid phase, each phase comprising a polymer blend. . 3. A process for producing a polymer blend by reacting at least one amino nitrile with water in the presence of a thermoplastic polymer and optionally other polyamide-forming monomers, comprising: (1) 90-400 ° C. Reacting at least one kind of aminonitrile with water at a temperature of 0.1 to 35 × 10 ⁶ Pa to obtain a reaction mixture. (2) further adding β-zeolite to the reaction mixture Catalyst, plate silicate catalyst,
Or 70 to 100% by weight of anatase and 0 to 30% by weight of rutile;
In the presence of a Brönsted acid catalyst selected from titanium dioxide catalysts whose mass% may be replaced by tungsten oxide, the reaction is carried out at a temperature of 150 to 400 ° C. and a pressure lower than that of step (1), The temperature and pressure are selected so as to obtain a first gas phase and a first liquid phase or a first solid phase, or a mixture of the first solid phase and the first liquid phase, and Separating a first gas phase from a first liquid phase, a first solid phase, or a mixture of the first liquid phase and the first solid phase; and (3) the first liquid phase or the first liquid phase. 1 or a mixture of a first liquid phase and a first solid phase at a temperature of 200 to 350 ° C. at a lower pressure than in step (2), wherein the temperature and pressure are: A second water- and ammonia-containing gas phase and a second
Selecting a liquid phase or a second solid phase, or a mixture of a second liquid phase and a second solid phase, wherein each phase comprises a polymer blend. A production method characterized by adding the thermoplastic polymer and, if necessary, other polyamide-forming monomers in the above steps. 4. The thermoplastic polymer is selected from polyarylene ethers, polyetherimides, polyamideimides, styrene homopolymers and copolymers, rubber elastic graft copolymers, ethylene copolymers, polyamides and mixtures thereof. The method according to claim 1. 5. The method according to claim 1, wherein the proportion of aminonitrile is 30 to 100% by mass based on the polyamide-forming monomer. 6. The method according to claim 1, wherein the content of the thermoplastic polymer in the reaction mixture is 1 to 75% by mass based on the whole reaction mixture. 7. The reaction of the step (1), (2) and / or (3) is performed by using a β-zeolite catalyst, a plate-like silicate catalyst, or 70 to 100% by mass of anatase and 0 to 30% by mass of rutile. The method according to any one of claims 1 to 6, wherein the method is carried out in the presence of a Bronsted acid catalyst selected from titanium dioxide catalysts which may be substituted with up to 40% by mass of tungsten oxide. 8. An aminoalkyl nitrile containing an alkylene moiety having 4 to 12 carbon atoms (—CH ₂ —) or an aminoalkylaryl nitrile having 8 to 13 carbon atoms is used as the amino nitrile. The method according to any of the above. 9. A polymer blend obtained by the method according to claim 1. 10. Use of the polymer blend according to claim 9 for producing fibers, films or moldings. 11. A fiber, film or molded article comprising the polymer blend according to claim 9.